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Submitted to
Dr.A.Kasi.Vishwanath
Reader
Center for Nanoscience & Technology
Submitted By
Rosalin Beura
M.Tech(NST) 1
st
yr
NST-611
Introduction to Nanotechnology
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Outline

INTRODUCTION
CATALYSTS
NEED FOR NANOCATALYSTS
PREPARATION METHODS
CURRENT TECHNOLOGY
APPLICATIONS
REFERENCES



Nanorust cleans arsenic from drinking water.
(Image courtesy of Rice University
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Catalysis
Catalysis is the change in rate of a chemical reaction due to the
participation of a substance called a catalyst.
Unlike other reagents that participate in the chemical reaction, a
catalyst is not consumed by the reaction itself.

What is catalyst ?
A catalyst is a substance other than reactants ,products added to a reaction
system to alter the speed of a chemical reaction approaching a chemical
equilibrium.
A catalyst changes the activation energy, E
a
, of a reaction by providing an
alternate pathway for the reaction.
k = A exp (
- E
a
/
R T
)
Where, k= rate of reaction
A= constant related to collision rates
E
a
=Activation energy
R=Rydberg constant
T=temperature


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A catalyst may participate in
multiple chemical transformations

Increase reaction rate= positive catalysts
slow reaction rate= inhibitors
Substances that increase the activity of catalysts= promoters
Substances that deactivate catalysts activity= catalytic
poisons.
http://www.rsc.org/images/distillates
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Generic potential energy diagram showing the effect of a catalyst in a hypothetical exothermic chemical reaction X + Y
to give Z. The presence of the catalyst opens a different reaction pathway (shown in red) with a lower activation
energy. The final result and the overall thermodynamics are the same.
How does a catalyst works?
Changes the activation
energy----by offering an
alternative pathway----
which requires less K.E.
in molecular collision
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Types of Catalysts
Heterogeneous
Acts in the different medium
from that of the reactant
Homogeneous
Acts in the same medium
as that of the reactant
Mostly solids that act on substrates in
a liquid or gaseous reaction mixture
Typically homogeneous
catalysts are dissolved in a
solvent with the substrates
Eg. Haber process

H
2
+3N
2
2NH
3
Eg.influence of H
+
on the
esterification of esters, methyl
acetate from acetic acid and
methanol
Fe
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Other catalysts
Electrocatalysts
Generally in electrochemistry= fuel cell engineering

Eg.- Platinum nanoparticles supported on slightly larger carbon
particles. When in contact with one of the electrodes in a fuel cell, this Pt
the rate of oxygen reduction to water, either to hydroxide or hydrogen
peroxide.

Organocatalysis
Small organic molecules without metals exhibits catalytic properties,
apparent from the fact that many enzymes lack transition metals

The discipline organocatalysis is divided in the application of
covalent (e.g., proline) and non-covalent (e.g., thiourea organocatalysis)
organocatalysts referring to the preferred catalyst-substrate binding and
interaction, respectively.

Autocatalysts- catalysis in which the catalyst is one of the products of
the reaction
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Some catalysts
Fuel catalyst
Reactor with IC-47catalyst
Catalytic Convertor
Ceramic catalyst
used in industry
Bio catalyst
Diesel enginebased construction
equipment, a large potential application for
the nanocatalyst technology.
Alps Bio Cluster Catalyst event
on "Biotherapy and Diagnostics"
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Basic Principles of chemistry

For any chemical reaction to occur, two reactive
species must come in contact with each other.
Why nanocatalysts is so promising ??
The total surface area of solid has an important effect on the
reaction rate. The smaller the catalyst particle size, the larger
the surface area for a given mass of particles.
http://nanocat.kaust.edu.sa/PublishingImages/KCC
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Key concept to understanding nanocrystal catalysis
involves the ratio of surface area and volume.
2

i
n
c
h
e
s

2 inches
Volume=8 cubic inches
Surface area=24 sq. inches
Surface :Volume =24:8=3
Volume=1cubic inch
Surface area=6 sq. inches
Surface :Volume =6:1=6
1

i
n
c
h

1 inch
Surface to volume ratio increases with reducing the size
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Nanocatalysts

A Nanocatalyst is a substance or material with catalytic
properties that has at least one nanoscale dimension, either
externally or in terms of internal structures
.
Generally, catalysts that are able to function at atomic scale
are Nanocatalysts.

Nano-materials are more effective than conventional catalysts for
two reasons.
Extremely small size (typically 10-80 nanometers) yields a
tremendous surface area-to-volume ratio.
Materials fabricated on the nanoscale achieve properties
not found within their macroscopic counterparts.

Both of these reasons account for the versatility and
effectiveness of nanocatalysts.
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The chart below represents the number of the
publish reports on nanostructured metal catalyst

http://www.bepress.com/cgi/viewcontent.cgi?article=2132&context=ijcre
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Specific metal catalyst
Interest in specific elements in the preparation of Nanoparticles in the period 2000-
2007
http://www.bepress.com/cgi/viewcontent.cgi?article=2132&context=ij
cre
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Early milestones in nanocatalysis
1. Refinery industry started the use of precious metal
platinum(Pt) as a reforming catalyst half century ago to
increase octane no of gasoline .
Bimetallic catalyst was made to increase the performance
and life of the catalyst.
Way to improve performance and reduce catalyst cost
Engineer smaller sized catalyst particles
Dispersion of catalyst metal in a desired way.

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2. Nanostructure catalysts:Zeolites
Zeolites were developed in 1960
Zeolites are special bcoz of their coustamizable cage
like structure .By changing the sizes of the hole in the
cage different molecules can be allowed to keep out
of the zeolite to only produce desired reaction thus
preventing formation of unwanted byproducts.
Zeolites are mainly used in refining application
http://www.google.co.in/search?q=zeolite
Zeolites
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Nanocatalysts
http://nanocat.kaust.edu.sa/Documents/nano-catalyst-
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SYNTHESIS TECHNIQUES
Micellar Chemical Vapor Deposition
Hydrothermal processing
High-energy ball milling Microemulsion
Sol-gel Plasma
Out of all the above methods, Advantages of Sol-gel &
hydrothermal synthesis are :
Produce materials at low temperatures
Produce commercially viable quantities relatively cheap
Synthesize single, binary or more material systems
Produce extremely homogeneous composites
Precisely control the physical, chemical and mechanical
properties of the final products

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Current technology
The control of catalyst nanoparticles size ,composition,
dispersion , crystal structure exposure and stability is the
key to producing pure ,efficient and strong catalysts and
from marketing perspective ,it is crucible to be able to
control these features at low or competive cost.

Ultimately to meet both the scientific requirements the
catalyst must be highly selective ,highly active and
unerringly stable and the market imperative the
production must be cost effective .


arabianoilandgas.com
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atoms size =no of precious particles less cost .
1. Controlling Size:Nanoparticle catalysts
Conventional catalyst contains small nanoparticles ,along with the
mixture of much larger particles.
Eg.20nm particles contains 384,000 atoms of precious metal
3 nm particle contains 1,300 atoms i.e. 300 times fewer
Exposed surface=active part & inner part value is lost.


Controlling size desired result can be generate thus eliminating
the waste.
Current method for preparing the nanosize distribution are
Dendrimer control method
Surfactant use method
2. Composition control
Single metals are used successfully for many catalysts. Use of
multiple metal increase the strength of the catalyst
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3. Controlling Structure
Conventional chemical catalysts were made of active
nanoparticles with combination of different crystal
structures.nanotechnology controlling the catalysts structure
allows the exposure of the desired crystal structure ,and thus
resulting desired reaction.
Eg. Molecular sieve materials as MCM-41
http://www.google.co.in/imgres?q=molecular+seive
+material+MCM-41
MCM-41
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4. Achoring nanoparticles and Nanostructure Catalysis
The ability to make smaller nanoparticles is a big challenge,
since nanoparticles tend to agglomerate into larger
particles.This can be prevented by using chemical or polymer
templets to stabilize the particles.This Anchoring method
increase the life time of the catalyst.
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Application
Carbon nanotubes
Water purification
Bio diesel production
Fuel cell application
In drug delivery
Photocatalytic activity
In solid rocket propellants
TiO2 in energy application
Thin film solar cell
Waste water treatment
In environment protection
Nano catalyst
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Waste water treatment
For special industrial wastewaters contaminated with
traces of halogenated organic compounds (HOCs)
conc
n
which are nevertheless large enough to make a
discharge into municipal sewage works impossible.
The idea to detoxify the water by a selective
destruction of the HOCs by hydrodehalogenation
(HDH) reactions on palladium-containing nano-
catalysts.
RX + H
2
RH + HX

Extremely active palladium catalysts were generated on the basis of
ferromagnetic carrier colloids. The ferromagnetism of the carriers
enables a separation of the catalysts from the treated water by means of
magneto-separation.
Pd-Catalyst
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Biodiesel production
The general method for the preparation of biodiesel is
trans esterification reaction of oil and alcohol with
homogeneous catalyst.
The catalyst is well used to convert the oil with higher acid
value into biodiesel.
It is porous with particle sizes of 30100 nm.
The high specific surface area and large pore size are
favorable for contact between catalyst and substrates,which
effectively improved efficiency
of trans esterification.
Production of biodiesel from
Chinese tallow seed oil has
positive impact on the
utilization of agricultural and
forestry products.
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In environment protection
Sulfate radical-based advanced oxidation technologies
(SRAOTs) are attracting considerable attention due to the high
oxidizing ability of SRs to degrade organic pollutants in
aqueous environments.

Typically, a mature landfill leachate contains high levels of non-
biodegradable organics and ammonia nitrogen. Simultaneous
removal of the both persistent pollutants is a challenge. Scientific
study to apply a sulfate radical (SO(4)(-))
-based advanced oxidation
process to treat a mature
leachate, with an emphasis
of concurrent removal of
refractory organics and
ammonia
http://www.sciencedirect.com/science/article
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Photocatalysis
Photocatalysis is the acceleration of a photoreaction in the
presence of a catalyst. Here photocatalytic activity (PCA) depends
on the ability of the catalyst to create electronhole pairs,
which generate free radicals (e.g. hydroxyl radicals: OH) able
to undergo secondary reactions.For this we need a
semiconductor.
The parameters of the photocatalysts that control the efficiency
of the reaction are morphology,specific surface area,particle size,
crystal phase,surface defects etc.
From the available semiconductor
TiO
2
is so far the most useful.
It exists in two forms
anatase(3.23) & rutile(3.02) .
This energy gap combine with
The valence band position
to generate highly energetic holes
giving rise to easy oxidation reaction.
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In nanocrystalline substance the alteration of the band gap to
larger value facilitates the oxidation /reduction reaction which
cannot be proceeded in bulk semiconductor.
The change in the surface atoms results in the increase in the
surface energy.
Reduction of particle size increase in the energy of formation of
electron hole pair and shifts the conduction and valence band
towards more negative & more positive potential
respectively.Increase in band gap favours the water splitting &
oxidation of organic compounds
that have slightly higher potential
than the potential of valence bond in the bulk.
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R&D INVESTMENT AND IMPLEMENTATION
STRATEGIES
In 2009 WTEC (World Technology Evaluation Center )catalysis report
(Davis et al.2009) noted that the overall level of investment in
catalysis research in Europe appears to be higher than that in US.
The report noted that Europeans and Asians countries have done
excellent job combining academic research with national labrotary
activities.
The ability to monitor catalysts with the appropiate resolutio in their
working state is critical to understanding & thus control of nanoscale
cataysts .
Nanostructured catalysis has the potential to profoundlly
affect our quality of life & should be reflected through
investment in research & development in this area.
The two challenging factors in the area for
nanotechnology for catalysis are
Predictive design &fabrication of bulk catalystparticles with
nanongineered porosity over multiple length scale.
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Conclusion
The field of nanocatalysis (the use of nanoparticles to catalyze
reactions) has undergone an explosive growth during the
past decade, both in homogeneous and heterogeneous
catalysis.
Nanoparticles have a large surface-to-volume ratio compared to
bulk materials, they are attractive to use as catalysts. Catalysts
daily accelerate and boost thousands of different chemical
reactions, and thereby form the basis for the multibillion
dollar chemical industry worldwide and indispensable
environmental protective technologies.
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References
1. Applications of nano-catalyst in new era
Shalini Chaturvedi a, Pragnesh N. Dave a,*, N.K. Shah b, Journal of Saudi Chemical
Society (2012) 16, 307325
2. NOVEL NANO-CATALYSTS FOR WASTEWATER TREATMENT, Global NEST
Journal, Vol 10, No 1, pp 47-53, 2008
3. Global NEST Journal, Vol 10, No 1, pp 47-53, 2008,
Int. J. Electrochem. Sci., 6 (2011) 4572 - 4580
4 .Nanocrystals: Solution-Based Synthesis and Applications as Nanocatalysts
Nano Res (2009) 2: 30 46
5 Local Ordering Changes in PtCo Nanocatalyst Induced by Fuel Cell
Working Conditions Giorgia Greco, Agnieszka Witkowska
6.Nanoparticles and Nanostructure Catalysis:Technologies and Markets-Bing
Zhou,Ray Balee,Rebecca Groenendaal

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